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Tiêu đề Standard Practice For Designing And Validating Performance-Based Test Methods For The Analysis Of Metals, Ores, And Related Materials
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Designation E 2437 – 05 Standard Practice for Designing and Validating Performance Based Test Methods for the Analysis of Metals, Ores, and Related Materials1 This standard is issued under the fixed d[.]

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Standard Practice for

Designing and Validating Performance-Based Test Methods

This standard is issued under the fixed designation E 2437; the number immediately following the designation indicates the year of

original adoption or, in the case of revision, the year of last revision A number in parentheses indicates the year of last reapproval A

superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1 Scope

1.1 This practice covers a model for designing and

validat-ing performance-based, ISO 17025-compliant, standard test

methods for the instrumental chemical analysis of metals, ores,

and related materials The principles in this practice can also be

applied to the development of test methods used to determine

the composition of other materials

1.2 This standard does not purport to address all of the

safety concerns, if any, associated with its use It is the

responsibility of the user of this standard to establish

appro-priate safety and health practices and determine the

applica-bility of regulatory limitations prior to use.

2 Referenced Documents

2.1 ASTM Standards:2

E 135 Terminology Relating to Analytical Chemistry for

Metals, Ores, and Related Materials

E 305 Practice for Establishing and Controlling

Spectro-chemical Analytical Curves

E 691 Practice for Conducting an Interlaboratory Study to

Determine the Precision of a Test Method

E 1329 Practice for Verification and Use of Control Charts

in Spectrochemical Analysis

E 1601 Practice for Conducting an Interlaboratory Study to

Evaluate the Performance of an Analytical Method

E 1621 Guide for X-Ray Emission Spectrometric Analysis

E 2027 Practice for Conducting Proficiency Tests in the

Chemical Analysis of Metals, Ores, and Related Materials

E 2165 Practice for Establishing an Uncertainty Budget for

the Chemical Analysis of Metals, Ores, and Related

Materials

2.2 ISO Standards 3

ISO 17025 General Requirements for the Competence of Testing and Calibration Laboratories

ISO Guide 31 Reference Materials—Contents of Certifi-cates and Labels

ISO Guide 32 Calibration in Analytical Chemistry and Use

of Certified Reference Materials

ISO Guide 34 General Requirements for the Competence of Reference Material Producers

3 Terminology

3.1 Definitions—For definitions of terms used in this

prac-tice, refer to TerminologyE 135

3.2 Definitions of Terms Specific to This Standard: 3.2.1 aim interlaboratory uncertainty, n—the maximum

deviation (95 % confidence) to be allowed in the design of the total interlaboratory uncertainty of a test method, beginning with the preparation of a homogeneous sample and ending with

a final report value to the client

3.2.2 aim uncertainty budget, n—during the development of

a standard performance-based test method, the target allocation

of interlaboratory measurement uncertainty among specific components of a measurement process that contribute signifi-cantly to the overall deviation

3.2.2.1 Discussion—The target allocation is made by the

task group as described in Practice E 2165 and serves as guidance for interlaboratory test participants during method testing

3.2.3 interlaboratory uncertainty, n—in a performance

based standard test method, the precision (95 % confidence) that participating laboratories achieved during interlaboratory studies, beginning with the preparation of a homogeneous sample and ending with a final report value to the client

3.2.4 intralaboratory uncertainty, n—in a performance

based standard test method, the precision (95 % confidence) that a laboratory achieves when the method is used by more than one operator In test methods that establish maximum allowable intralaboratory uncertainties, users must be able to demonstrate compliance with those uncertainties in order to report that a given test result was produced using the named method

3.2.5 performance based method, n—a test method that

defines (1) the general approaches for sampling, sample

1 This practice is under the jurisdiction of ASTM Committee E01 on Analytical

Chemistry for Metals, Ores, and Related Materials and is the direct responsibility of

Subcommittee E01.22 on Laboratory Quality.

Current edition approved May 1, 2005 Published July 2005.

2 For referenced ASTM standards, visit the ASTM website, www.astm.org, or

contact ASTM Customer Service at service@astm.org For Annual Book of ASTM

Standards volume information, refer to the standard’s Document Summary page on

the ASTM website.

3 Available from American National Standards Institute (ANSI), 25 W 43 rd St.,

4 th Floor, New York, NY 10036 (www.ansi.org).

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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preparation, and making measurements on a specified type of

material, and (2) defines maximum allowable uncertainties for

each measured constituent over its validated concentration

range

3.2.6 uncertainty budget, n—the allocation of

intralabora-tory measurement uncertainty among specific components of a

measurement process that contribute significantly to the overall

deviation

4 Significance and Use

4.1 This practice provides guidance for methods-writing

task group leaders and members in planning, drafting, and

testing performance-based test methods It also guides users of

performance-based methods in interpreting and applying them

properly

4.2 Standard test methods, particularly those that cover the

instrumental analysis of commercial materials by specific

measurement techniques, such as point-to-plane atomic

emis-sion, x-ray fluorescence, inductively-coupled plasma, and

atomic absorption spectroscopy, need sufficient flexibility to

accommodate the various applicable makes and models of

instrumentation At the same time, these standard test methods

must be capable of generating commercially-useful results that

are sufficiently accurate and precise These needs can be met by

the use of performance-based test methods that rely more on

the demonstrated quality of the test results than on strict

adherence to specific procedural steps One model for

devel-oping these methods is described in this practice

4.3 It is expected that laboratories using performance-based

standard test methods developed in accordance with this

practice will prepare their own detailed work instructions

These work instructions will include detailed operating

instruc-tions for the specific laboratory, the specific reference materials

(RMs) employed, and performance acceptance criteria to be

applied in that laboratory It is also expected that those

laboratories will document their own performance data using

their work instruction to show that their data are consistent

with the standard test method’s Precision and Bias statement

Over time, it is also expected that, when applicable, an

individual laboratory’s proficiency test results will also be

consistent with its documented performance

4.4 Traditional ASTM Precision and Bias statements,

devel-oped during interlaboratory testing in accordance with

Prac-tices E 691 and E 1601, provide information on the

perfor-mance achieved by participating laboratories Intralaboratory

precision can be estimated by dividing the Repeatability index,

r, in the Precision and Bias Table by the square root of 2, at any

tested concentration Proficiency test programs, such as those

following PracticeE 2027, periodically provide interlaboratory

performance data from larger numbers of laboratories, using a

variety of test methods, at many different concentrations over

an extended time period Since interlaboratory precision

ob-tained during both method development and proficiency testing

using existing methods is a function of concentration, per

PracticeE 2165, it follows that the interlaboratory testing of a

new test method should perform no worse than its

predeces-sors Practice E 2165describes how historical interlaboratory

test results can be used to set aim data quality objectives for

new test methods This practice incorporates those aim data

quality objectives in developing uncertainty budgets used in the design, development, and testing of performance-based methods This approach ensures that interlaboratory test data included in Precision and Bias statements are consistent with that associated with the other standard test methods

5 Summary of Practice

5.1 The remaining parts of this practice provide instructions for planning a performance-based method development project, conducting the necessary validation and interlabora-tory precision tests, and documenting the results

5.2 The organization of the rest of the practice guides the task group through the following steps:

5.2.1 Section 6—Sets overall objectives for the project, detailed only to the extent needed to convince the task group that the project can be accomplished as planned

5.2.2 Section7—Sets the technical parameters to be incor-porated in the new test method Establishes details needed to facilitate organizing and drafting a test method

5.2.3 Section8—Addresses writing the first draft of the test method

5.2.4 Section9—Describes how to verify the draft method before entering into more extensive interlaboratory testing 5.2.5 Section 10—Discusses writing the interlaboratory protocol plan so that all of the needed data is available in a form that is easily processed

5.2.6 Section11—Describes task group work in conducting the interlaboratory test

5.2.7 Section12—Describes performance-based method in-formation to be included in the Research Report

5.2.8 Section 13—Addresses finalizing the text of the test method after interlaboratory testing is satisfactorily completed

6 Setting Objectives

6.1 For the material to be tested, identify and list applicable national and international product specifications, sampling practices, and standard test methods Be sure to reference these documents appropriately in the new test method

6.2 List the elements and concentration ranges to be in-cluded in the materials to be analyzed using the method and list the subset of those elements and concentration ranges to be incorporated as analytes in the new test method

6.3 Determine how measurement uncertainty and data qual-ity objectives will be handled

6.3.1 To comply with ASTM requirements, plan to prepare

a precision and bias statement To comply with ISO 17025

requirements, plan to identify all significant sources of mea-surement uncertainty and to calculate the intralaboratory un-certainty (3.2.3) from the information in the precision and bias statement

6.3.2 To help laboratories use the new performance-based test method more effectively, the task group should consider developing an uncertainty budget (3.2.5) That budget may be developed as suggested in this practice, or in a different way, provided that the minimum requirements in6.3.1are met 6.3.3 If the task group elects to develop an uncertainty budget as described in this practice, it should attempt to establish each component of its aim uncertainty budget as defined in Practice E 2165 In some cases, the method of

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choice may not be optimum for each analyte to be covered In

those cases, if the anticipated performance meets applicable

specification requirements, the task group should set its data

quality objectives in a way that is compliant with specifications

(commercial needs) and attainable performance The

compo-nents of uncertainty will be useful in planning and developing

the performance-based test method

7 Setting Technical Parameters

7.1 Select the Approach to Make the Measurements:

7.1.1 Select a measurement technique that represents an

optimum choice based on: (1) wide acceptance and use

throughout the industry, (2) anticipated ability to measure all

elements and concentration ranges in conformance with the

aim uncertainty budget, (3) anticipated sustained availability of

Certified Reference Materials (CRMs) for achieving traceable

calibrations (Note 1) of all elements and concentration ranges,

and (4) anticipated sustained availability of homogeneous

materials needed for statistical control of the method

N OTE 1—This practice assumes the use of a Type III calibration as

defined in ISO Guide 32 Types I and II do not require the use of CRMs.

7.1.2 Select the sampling equipment and procedure

Re-solve any questions about the adequacy of the sampling

process Ensure its acceptability to users If a new or revised

sampling practice is needed, arrange for the development of

that practice and establish acceptability with those who are

responsible for performing the sampling

7.1.3 Select a sample preparation technique that is

compat-ible with the selected sampling and measurement technique

and current industry practices If a new or revised sample

preparation practice is needed, arrange for the development of

that practice as part of the new test method

7.2 Design the Measurement Approach:

7.2.1 Calibration Approach—Based on the measurement

technique selected in 7.1.1, determine if calibration is to be

achieved by matrix-matched CRMs or by laboratory-prepared

RMs that are traceable to CRMs Matrix-matched CRMs are

preferred, when available, and are most frequently used when

solid samples are analyzed RMs that are traceable to CRMs

are often used in test methods calibrated with solutions In

these cases, materials of known purity are added to CRM

solutions in order to match the overall composition of sample

solutions Refer toISO Guide 32for recommended approaches

to calibration using Certified Reference Materials

7.2.2 Data Quality Objectives—Set the aim intralaboratory

uncertainty (3.2.2) to be achieved in the new test method

Complete the aim uncertainty budget for all elements and

concentration ranges in accordance with the decisions made in

Section6 Refer toX1.2and PracticeE 2165for one approach

7.2.3 Calibration and Calibrants:

7.2.3.1 For each element and concentration range, ensure

the availability of sufficient numbers of acceptable calibrants

Sufficient numbers of calibrants must be available to define the

shape of each calibration curve over the concentration range of

interest and to allow compensation for interelement effects

Refer to Practice E 305 or Guide E 1621 for additional

background information An acceptable calibrant is a CRM that

is compliant withISO Guide 34, or an RM that is traceable to

a CRM or the appropriate SI unit, and has an estimated uncertainty small enough to make it possible to meet the aim data quality objectives of the method Some methods may be calibrated directly with CRMs used in the as-received condi-tion Others may require the dissolution of chip or solid CRMs

or the use of CRM spectrometric solutions that must be combined with other reagents or materials in order to provide suitable calibrants In cases where CRMs are combined with other reagents to make calibrants, the standard test method must provide strict specifications on those reagents to ensure that the calibrants’ assigned quantity values are accurate and have correct uncertainty estimates

7.2.3.2 Set aim uncertainty limits for all calibration curves and calibrants See X1.2.2.2 and X1.2.2.3 for a suggested approach

7.2.4 Verifiers—Ensure the availability of traceable

refer-ence materials that comply with the requirements of7.2.3, but are reserved for use to independently verify the calibration function

7.2.5 Quality Control—For each element and concentration

range to be determined, ensure the availability of material that can be used for control in accordance withISO 17025, clause 5.9 For planning purposes, consider the availability of at least two concentrations for each calibration range, one at about

20 % and one at about 80 % of the maximum values Avail-ability means that a typical laboratory can acquire the needed materials in a reasonable way, either commercially or in-house Establish aim uncertainty limits for each case SeeX1.2.2.1for

a suggested approach

8 Drafting the Method

8.1 Draft the standard test method in accordance with the ASTM Form and Style Manual, Part A, making sure to include the following information which is essential to a performance-based method Except for the intralaboratory performance requirement, the draft will include estimated uncertainty infor-mation consistent with the decisions made in Section6

8.2 Significance and Use—Emphasize that this is a

performance-based method and that each user is expected to create specific work instructions that describe how the performance-based method is applied in that laboratory Also, emphasize that the user laboratory is expected to have perfor-mance data taken in accordance with its work instructions to demonstrate that it meets the minimum data quality objectives specified in the standard test method

8.3 Interferences—In a performance-based method, it is not

practical to identify all possible interferences that may cause bias in the test results In drafting this section of the test method, the task group may identify common interferences and advise laboratories to take steps to avoid them Likewise, this section shall include a statement to the effect that the user laboratory is responsible for ensuring the absence of, or correcting for, interferences that may bias test results generated while following its specific work instructions

8.4 Apparatus—Identify the generic types of equipment

covered in the test method For example, “sequential and simultaneous X-ray fluorescence spectrometers capable of covering the elements and concentration ranges included in

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laboratory’s documentation and capable of meeting the

perfor-mance requirements specified in the method.” Also, include the

functionality required of sampling and sample preparation

equipment, as appropriate, taking care not to specify more

prescriptively than necessary to remain within the scope of the

method

8.5 Reference Materials, Reagents, and Related Materials.

8.5.1 Calibrants:

8.5.1.1 List the requirements for calibrants and give

instruc-tions for selecting them When defining the requirements for

calibrants, refer to the decisions made in 7.2, while trying to

avoid, if possible, specifying the use of specific CRMs

8.5.1.2 For a comparative method to be calibrated using

CRMs, identify the qualities needed in the calibrants, such as:

“Select sufficient numbers of certified reference materials that

are supplied by National Metrology Institutes or are certified to

comply with ISO Guides 31 and 34 Cover all elements and

concentration ranges and allow for the correction of

interfer-ences, as needed.” The standard test method should not specify

which specific CRMs to use because the test method will

become invalid when those specific CRMs no longer exist

Similarly, new CRMs that become available after the method is

published would not be included If, for some reason the use of

a specific CRM is unavoidable, include language that allows

the use of its replacement

8.5.1.3 For a method to be calibrated using solutions or pure

chemicals, describe how to obtain or prepare calibrants that

meet the traceability requirements without creating bias by the

addition or loss of analyte concentration

8.5.1.4 If the task group elects to develop a full uncertainty

budget in accordance with Appendix X1, or an alternative

approach, refer to the maximum aim uncertainty to be allowed

for the calibrants as a function of concentration

8.5.2 Verifiers—Specify the requirements for verifiers that

meet the requirements of8.5.1but specify that they not be used

as calibrants Require that verifiers be analyzed as unknowns

immediately after the calibration is complete Since verifiers

are used to confirm the accuracy of the calibration process, the

limits of uncertainty for the verifiers and the verification

process are the same as for the calibrants and the calibration

process

8.5.3 Standardization Materials—If the method requires

standardization (drift correction), give requirements for the

selection and management of the materials Consider the effect

of standardization on the final report value and establish

criteria that are consistent with the acceptable intralaboratory

precision It is not necessary to establish specific limits of

acceptability for the standardization procedure because these

sources of variation are included in the control process

8.5.4 Quality Control— Specify the requirements for

estab-lishing the number and concentration of control samples, as

needed Concentrations need not be certified, but homogeneity

should be established and should be about the same level as the

calibrants If the use of control charts is to be specified, refer to

Practice E 1329

8.5.5 Reagents:

8.5.5.1 Water—If water is used in the test method and the

purity of the water might influence the quality of the test

results, specify the purity requirements Pay particular attention

to setting analyte concentrations that, if exceeded, and not corrected for, could cause bias in the test results

8.5.5.2 Chemicals—If specific chemicals, liquids, solids, or

gases, are to be used in the test method, list them and their required purities If the laboratory has the option to select its own chemicals, give generally applicable specifications If no chemicals are to be used in the test method, skip this section

8.6 Procedure:

8.6.1 Sampling of lots of materials, whether conducted by laboratory-supervised personnel or not, is usually considered outside the scope of an ASTM test method However, for some materials, laboratories may be required to subdivide the as-received sample in order to perform the required tests Such sub-divisions should be considered and described in the test method

8.6.2 Indicate the major steps that must be accomplished to generate a report value Refer to manufacturer’s instructions and individual user’s work instructions for details

8.6.3 Discuss and explain the criteria of acceptance that must be met if a report value is to be supplied in association with the Standard Test Method See X1.2.1 for a suggested approach State the intralaboratory data quality objectives plus any measurement uncertainty requirements that must be met and documented by the laboratory, whether reported to the client or not

8.7 Precision and Bias:

8.7.1 Write this section after completion of the interlabora-tory test program, as required by standard ASTM protocols, including PracticesE 1601andE 691

8.7.2 Add a section that summarizes the derivation of the intralaboratory test data and any detailed measurement uncer-tainty budget requirements the task group elected to include in the method Use Appendices and Annexes as appropriate

8.8 Report:

8.8.1 Require that a laboratory comply with all require-ments, including data quality of the standard test method in order to state on a test report that the test result was generated using this test method Require the laboratory to comply with all reporting requirements of ISO 17025

8.9 Annex or Appendices, or both:

8.9.1 Provide sufficient detail on how the uncertainty budget data was generated during the interlaboratory study and how the requirements summarized in the Precision and Bias state-ment shall be interpreted by laboratories that use the standard method Use either an Annex or an Appendix, as appropriate

9 Verifying the Drafted Method

9.1 Verification Laboratory—Select a competent laboratory

(one that complies with the applicable clauses ofISO 17025) which utilizes the measurement technique to analyze the material to be covered in the new standard test method Obtain sufficient performance data from that laboratory to demonstrate that the technique of choice can achieve the expected data quality objectives for all elements and concentration ranges, making sure to cover any which might be difficult to achieve

If the results from the selected laboratory cast doubt on the ability to achieve ultimate success, consider redesigning the proposed test method This step is primarily intended to

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provide design information to help the task group effectively

plan its work program Therefore, design details are left to the

task group

9.2 If the test materials and interlaboratory test protocol are

available as described in Section10, the task group may elect

to have the verifying laboratory perform the interlaboratory

study protocol as a test case If successful, the results of the

verifying laboratory may be used as a participating laboratory

in the final calculations

10 Drafting the Interlaboratory Test Protocol

10.1 Select Test Materials—Select test materials that cover

the elements and concentrations to be included in the new

method Make sure that suspected interferences are also

covered To the fullest extent possible, use CRMs that have

reliable uncertainty estimates available so as to be able to

demonstrate absence of measurable and correctable bias If the

test method includes sample preparation steps that might

influence the quality of the results, be sure to include some test

materials that need to be prepared by the participating

labora-tories and be prepared to evaluate the precision obtained on

these materials This will allow the task group to evaluate the

effects of sample preparation on the precision Be sure that the

homogeneity of all test materials is known, including CRMs

10.2 Introduction:

10.2.1 Explain that this test protocol covers the

develop-ment of a performance-based method and that the performance

of participating laboratories will be used in establishing the

data quality that all laboratories that will use the new method

will need to achieve in order to claim that they followed the test

method Explain that the Interlaboratory Study is based on Plan

A in PracticeE 1601and that all test materials are known to be

homogeneous

10.2.2 Explain that the aim data quality objectives included

in this work plan have been achieved by competent laboratories

using similar test methods over time and by at least one

competent testing laboratory using the draft method under test

10.2.3 Advise the participating laboratory that it is expected

that the aim data quality objectives should be met during the

formal interlaboratory test If the participating laboratory

cannot meet the aim data quality objectives, it should check the

function of its equipment, and if that fails, it should contact the

task group chairman immediately

10.3 Qualification of Participating Laboratories:

10.3.1 In order to avoid receiving sub-par data, it is

sug-gested that the task group ask the participating laboratory to

provide data that shows that it is capable of obtaining

accept-able data prior to actually conducting the test The task group

shall design the qualification test and request that the

qualifi-cation data be generated before conducting the interlaboratory

test The qualification data shall be submitted to the

coordina-tor no later than with the final data package

10.3.2 Typical qualification packages might include

demon-stration of ability to achieve adequate signal/noise ratios,

demonstrated ability to calibrate over the concentration ranges

of interest, and sufficient measurement precision over the

anticipated concentration range to achieve the desired

analyti-cal performance In some cases these requirements might be

fulfilled by asking the participating laboratory to analyze

specified CRMs a given number of times, back to back, on one day, using the participating laboratory’s existing in-house procedure

10.3.3 In designing the qualification and final tests, the task group should be careful to give specific directions so that a laboratory will know immediately whether or not its measure-ment performance meets expectations In the event that the laboratory does not meet expectations, it has time to resolve the problem before spending time and resources on the official test

10.4 Instructions for Carrying Out the Interlaboratory

Study:

10.4.1 The instructions for conducting the interlaboratory test should be limited to the test itself and should not alter any instructions in the draft test method Give instructions to assist the task group with evaluation of data, for example, by providing data sheets Data sheets should make clear the number of significant figures to be supplied by participating laboratories Without such instructions, the task group may receive data in a form that is not optimum for statistical analysis Refer to Practice E 1601 for further instructions regarding statistical calculations

10.4.2 The following types of information might be rou-tinely required by the task group: (1) all pre-qualification data, (2) make and model of sample preparation and measuring equipment, the use of which might affect data quality, (3) list of CRMs used for calibration, with copies of certificates for each showing measurement uncertainties, (4) Calibration records showing the degree of curve fit and calibration measurement uncertainty, (5) list of RMs used for control and standardiza-tion, as appropriate, with documentation showing their homo-geneity, (6) all test data used to calculate each report value included in the interlaboratory test, and (7) statements relating

to compliance with aim quality objectives

10.4.3 Provide information on the measurement uncertainty expectations being placed on the cooperating laboratories and provide resources to contact with questions

10.4.4 Ask for comments from the participating laboratory 10.4.5 Set a deadline for submission of all test results to the task group chair

11 Conducting the Interlaboratory Test

11.1 For each participating laboratory, prepare a packet containing: (1) a cover letter (optional, but recommended), (2) the drafted method, (3) instructions for the interlaboratory test, (4) report forms, including data sheets, and (5) test samples Refer to Practice E 1601 for background on conducting an interlaboratory test

11.2 Receive data sets and comments from all participating laboratories

11.2.1 Review the qualification data from each laboratory to ensure that the laboratory was able to meet the general competency requirements associated with the test If the qualification data is not acceptable, contact the laboratory and resolve the issues before evaluating the test method data The availability of qualification data helps ensure that measurement uncertainties calculated as a result of the interlaboratory test are representative of competent laboratories If the qualifica-tion data is satisfactory, but the quality of the test data is not, there may be good reason to question the draft test method

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11.3 Prepare a Precision and Bias table and statement in

accordance with ASTM requirements Refer to Practices

E 1601 or E 691 Add a brief statement that defines the

maximum intralaboratory precision that a laboratory can

achieve and still be able to report results in accordance with the

new standard test method

11.4 If the task group elected to include a measurement

uncertainty budget as part of the test method, add an additional

section to the Precision and Bias statement that describes the

maximum uncertainty that a laboratory can achieve at each step

and refer to the appropriate appendix/annex for details

12 Writing the Research Report

12.1 Prepare the Research Report, covering all ASTM

requirements and discussing fully the derivation of

measure-ment uncertainty data, as described below

12.2 Summarize the pre-qualification data so that the official

record of the test method will contain evidence that the

participating laboratories were capable of performing the test

method Exclude the data from any non-compliant laboratories

from further evaluation

12.3 For each element in each test sample, calculate the

parameters required in Practice E 1601 Prepare the usual

Precision and Bias Table

12.4 For each element on each test sample, calculate the

interlaboratory precision, 95 % confidence, as described in

PracticeE 1601 Divide by the square root of 2 to estimate the

intralaboratory precision Compare the intralaboratory

preci-sion values with the aim data quality objectives If acceptable,

draw a best fit line through the points on a log-log plot, and create a smoothed data table for each element, or, preferably, for all elements, if appropriate This relationship defines the required intralaboratory performance (95 % confidence), that must be demonstrated in order to report that a set of test results were generated using the new standard test method

12.5 If the task group wrote the test method including an uncertainty budget, perform calculations as described in 6.3.3

for control, calibration, and reference materials

13 Finalizing the Method

13.1 Review and revise the draft method as needed for accuracy and completeness according to the usual ASTM procedures as supplemented by this practice

13.2 Provide the Precision and Bias section Add a section

to the Precision and Bias section defining the intralaboratory performance requirements as calculated in 6.3.3 Add a sen-tence indicating that a laboratory that uses this method must meet these performance criteria in order to claim that a report was generated using this test method

13.3 If an uncertainty budget is included in the method, provide a summary of those requirements either as a separate section or as an appendix or annex, as appropriate One acceptable way to present the numerical data is in the form of

a Table, similar to that shown in PracticeE 2165

14 Keywords

14.1 analytical chemistry; measurement uncertainty; mea-surement uncertainty budget; performance-based test method

APPENDIX (Nonmandatory Information) X1 Suggested Means for Establishing Aim Measurement Uncertainties for Performance-Based Methods and Confirming Them

During Interlaboratory Testing X1.1 Introduction

X1.1.1 As described throughout this practice,

performance-based methods rely much more heavily on the quality of the

test results than on obedience to prescriptive experimental

procedures It follows that those who write performance-based

standard test methods must be able to clearly define acceptable

performance This practice defines acceptable performance as

the intralaboratory precision (95 % confidence) obtained

dur-ing interlaboratory testdur-ing It then provides one approach for

task groups to incorporate model uncertainty budgets in

standard test methods, also in harmony with PracticeE 2165

X1.1.2 A primary advantage associated with the use of this

uncertainty practice in conjunction with the aim uncertainties

given in PracticeE 2165is that the task group will be assured

that its aim uncertainty objectives are comparable to other

standard test methods and to proficiency test performance in

general This means that laboratories that participate in the

interlaboratory testing can be reasonably confident that the aim

uncertainties set by the task group are reasonable and

achiev-able It also means that test results achieved by the laboratories

that use the test method will comply with general good laboratory practice and that the laboratory’s results submitted

to proficiency test programs will be consistent with other participants and other test methods

X1.1.3 If the task group sets data quality objectives that are less stringent than those identified in Practice E 2165, then there is a lower probability that laboratories that use the method and contribute to proficiency tests that include other test methods, will perform as predicted by the model

X1.2 A Model for Establishing Aim Data Quality Objectives

X1.2.1 Intralaboratory Precision—The task group should

establish acceptability criteria for intralaboratory precision as guidance for the cooperators in the interlaboratory test For any concentration, this value can be calculated as described in Practice E 2165 Be sure to report the results as 95 % confi-dence in order to comply with ISO 17025

X1.2.2 Uncertainty Budget—It has been shown that the

performance (precision without bias) obtainable by competent

Trang 7

laboratories performing optimized, state-of-the-art methods

can be described by a straight line on a log-log plot of

performance vs concentration4This model has been verified

using both proficiency test data and interlaboratory testing of

new standard methods of analysis A scheme for applying these

principles to uncertainty budgets is provided in Practice

E 2165 This document applies those principles to writing

performance-based standard test methods

X1.2.2.1 Control—Divide the intralaboratory precision by

the square root of 2 to find the aim uncertainty for the use of

control materials when performing the test method Note that

the aim control uncertainty is expressed as 2 sigma or 95 %

confidence It may be helpful to interpret control charts using

the Westgard Rules as described in PracticeE 1329

X1.2.2.2 Calibration—Divide the aim uncertainty for the

control function by the square root of 2 to find the aim

uncertainty for the calibration function This may be

inter-preted as the maximum difference between the assumed true

value of any calibrant and the calculated curve fit through that

point For purposes of assessing the calibration uncertainty, the

task group may assume that, because the curve fit is a

calculated function that averages responses from several

ref-erence materials, all points along the calibration curve should comply with the 95 % confidence

X1.2.2.3 Calibrants—Divide the aim uncertainty for the

calibration function by the square root of 2 to find the aim uncertainty at the assumed true concentration value for each calibrant

X1.3 Confirming the Measurement Uncertainty Budget during Interlaboratory Testing

X1.3.1 If the task group has determined that a full uncer-tainty budget is to be included in the standard test method, each aim uncertainty budget item shall be included in the Interlabo-ratory Study work plan so that each laboInterlabo-ratory knows that it is expected to meet or exceed these uncertainties during its testing of the method

X1.3.2 When all test results are in, the task group will compare the aim uncertainties with the experimentally deter-mined values and then adjust the uncertainty budget values as necessary However, if the experimentally obtained uncertain-ties are significantly worse than the aim values (confirmed during verification testing), there is reason to believe that the new test method may not be fully optimized and that further revision is needed

X1.3.3 The data, the findings, and an explanation of deci-sions made shall be included in the Research Report A summary shall be included in the test methods for use by laboratories in implementing the new test method

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned

in this standard Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk

of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and

if not revised, either reapproved or withdrawn Your comments are invited either for revision of this standard or for additional standards

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This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,

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address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website

(www.astm.org).

4 D A Flinchbaugh, L F Crawford, and D Bradley, “A Model to Set

Measurement Quality Objectives and to Establish Measurement Uncertainty

Expec-tations in Analytical Chemistry Laboratories Using ASTM Proficiency Test Data,”

Accreditation and Quality Assurance, (2001) 6:493-500.

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